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  • Physical Chemistry  (14)
  • Wiley-Blackwell  (14)
  • Institute of Physics
  • International Union of Crystallography
  • International Union of Crystallography (IUCr)
  • 1985-1989
  • 1980-1984  (14)
  • 1970-1974
  • 1940-1944
  • 1984  (14)
  • 1942
Collection
Publisher
  • Wiley-Blackwell  (14)
  • Institute of Physics
  • International Union of Crystallography
  • International Union of Crystallography (IUCr)
Years
  • 1985-1989
  • 1980-1984  (14)
  • 1970-1974
  • 1940-1944
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1027-1051 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the basic hydrolysis of glyceryl trinitrate (TNG) were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. TNG hydrolyzed via second-order reaction at 25°C, 18°C, and 10°C. The activation energy of the hydrolysis reaction of TNG was calculated from the kinetic data and found to be equal to 27.53 kcal/mol. The major products of the hydrolysis of TNG in solution of calcium hydroxide were calcium nitrate and calcium nitrite, accounting for approximately 50% of the degradation products. The minor identified products such as calcium oxalate and nitrate esters amounted to approximatey 6% of the products. The remaining 30% of the isolated products was a mixture of calcium formate, a nitrate ester, and unidentified volatiles, polymerlike substances, and other organic residue.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1139-1150 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular decomposition of methyl nitrite in the temperature range 680-955 K and pressure range 0.64 to 2.0 atm has been studied in shock-tube experiments employing real-time absorption of CW CO laser radiation by the NO product. Computer kinetic modeling using a set of 23 reactions shows that NO product is relatively unreactive. Its initial rate of production can be used to yield directly the unimolecular rate constant, which in the fall-off region, can be represented by the second-order rate coefficient in the Arrhenius form: \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 10^{17.90 \pm 0.21} \exp (- 17200 \pm 400/T){\rm cm}^{\rm 3} {\rm mol}^{ - 1} {\rm s}^{ - 1}$$\end{document} A RRKM model calculation, assuming a loose CH3ONO≠ complex with two degrees of free internal rotation, gives good agreement with the experimental rate constants.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1009-1026 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the basic hydrolysis of 1,2-glyceryl dinitrate (1,2-DNG) and 1,3-glyceryl dinitrate (1,3-DNG) esters were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. Both glyceryl dinitrate esters hydrolyzed via second-order reaction at 25°C. 1,2-DNG in basic solutions isomerized to 1,3-DNG which subsequently hydrolyzed to yield products. The main hydrolysis product of 1,3-DNG was identified as glycidyl nitrate. Other products formed during the basic hydrolysis of DNGs were nitrites and nitrates.
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 977-993 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemiluminescence from the a1Δ and b1Σ+ excited electronic states of nitrogen halide diatomics is observed when HN3 is allowed to react with mixtures of halogen atoms in a discharge-flow apparatus. Excited NF (a1Δ) is produced by the F + HN3 reaction, and NCl (a1Δ, b1Σ+) and NBr (a1Δ, b1Σ+) are produced by the F, Cl, + HN3 and F, Br + HN3 reactions, respectively. In the low-density limit, the yield of NF(a1Δ) was found to be near unity. The yields of the b1Σ+ states of NCl and NBr were determined to have a lower limit of ca. 10%. A number of results from these experiments, including direct observation of N3 radicals in the flow, support a hypothetical mechanism in which N3 acts as an intermediate. A second possible mechanism proceeding via an HNF intermediate cannot be ruled out.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1129-1137 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A readily applicable empirical formula is obtained for the collisional efficiency for energy transfer between a highly vibrationally excited reactant and a seasoned (usually quartz) wall, in terms of the molecular weight, potential well depth and dipole moment of the reactant. This expression is used to examine corrections due to nonunit wall collision efficiency in the high-pressure rate parameters obtained from very low-pressure pyrolysis experiments. It is found that these corrections are up to ca. ±5 kJ/mol in the high-pressure activation energy and a factor of ca. 2 in the high-pressure frequency factor, for molecules with molecular weight less than ca. 100 and where experiments are carried out at temperatures exceeding 1000 K.
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1623-1636 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of OH reactions with 1-4 carbon aliphatic thiols have been investigated over the temperature range 252-430 K. OH radicals were produced by flash photolysis of water vapor at λ 〉 165 nm and detected by time-resolved resonance fluorescence spectroscopy. All thiols investigated react with OH at nearly the same rate; k(298 K) = 3.2-4.6 × 10-11 cm3 molecule-1 s-1, -Eact = 0.6-1.0 kcal/mol, A = 0.6-1.2 × 10-11 cm3 molecule-1 s-1. CH3SH and CH3SD react with OH at identical rates over the entire temperature range investigated. We conclude that the dominant reaction pathway is addition to the sulfur atom.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 7-21 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase decompositions of methylsilane and methylsilane-d3 have been investigated in a single-pulse shock tube at 4700 torr total pressure in the temperature range of 1125-1250 K. For CH3SiD3 at 1200 K three primary steps occur in the homogeneous decomposition with efficiencies in parentheses: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm SiD}_{\rm 3} \mathop {\longrightarrow} \limits^1 {\rm CH}_{\rm 3} {\rm SiD} + {\rm D}_{\rm 2} \left( {0.71} \right) $$\end{document}, \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm SiD}_{\rm 3} \mathop {\longrightarrow} \limits^2 {\rm CH}_{\rm 4} + {\rm SiD}_{\rm 2} \left( {0.15} \right) $$\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm SiD}_{\rm 3} \mathop {\longrightarrow} \limits^3 {\rm CH}_{\rm 2} \raise1pt\hbox{=\kern-3.45 pt=} {\rm SiD}_{\rm 2} \left( {0.14} \right) $$\end{document}. For CH3SiH3 at 1200 K the primary CH4 elimination efficiency is 0.09 while the total primary H2 elimination efficiency is 0.91. Minor product formations of C2H4, acetylene, dimethylsilane, and SiH4 are discussed.
    Additional Material: 4 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 31-39 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homogeneous gas-phase decomposition kinetics of methylsilane and methylsilane-d3 have been investigated by the comparative-rate-single-pulse shock-tube technique at total pressures of 4700 torr in the 1125-1250 K temperature range. Three primary processes occur: CH3SiH3 → CH3SiH + H2 (1), CH3SiH3 → CH4 + SiH2 (2), and CH3SiH3 → CH2 = SiH2 + H2 (3). The high-pressure rate constants for the primary processes in CH3SiH3 obtained by RRKM calculations are log (k1 + k3) (s-1) = 15.2 - 64,780 Cal/θ and log k2 (s-) = 14.50 - 67,600 → 2800 Cal/θ. For CH3SiD3 these same rate constants are log k1 (s-) = 14.99 - 64,700 cal/θ log k2 (s-) = 14.68 - 66,700 → 2000 cal/θ, and log k3 (s-) = 14.3 - 64,700 cal/θ.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 117-124 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The static vessel pyrolysis of bicyclo[2.2.2]octa-2,5,7-triene (barrelene) has been studied between 483 and 523 K. The products were acetylene and benzene (in equal quantities) with no other detectable C8H8 isomer (down to less than 1% of total). The time dependence fitted first-order kinetics, and the data are consistent with a homogeneous unimolecular reaction close to, if not at, its high-pressure limit at 0.25 torr. The rate constant was fitted to the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \left( {{k \mathord{\left/ {\vphantom {k {s^{ - 1} }}} \right. \kern-\nulldelimiterspace} {s^{ - 1} }}} \right)\, = \,\left( {14.27\, \pm \,0.18} \right)\, - \,{{\left( {41.71\, \pm \,0.41\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}} \right)} \mathord{\left/ {\vphantom {{\left( {41.71\, \pm \,0.41\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}} \right)} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}\,\ln \,10 $$\end{document} These Arrhenius parameters are shown to imply a concerted single-step process. Alternative mechanisms are discussed and a comparison is made with the retro-Diels - Alder reactions of other bicyclo[2.2.2]octa-olefin systems.
    Additional Material: 4 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 251-258 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the reaction of aqueous sulfite with the N-chloropeptide N-chloroalanylalanylalanine has been studied as a function of pH, temperature, and ionic strength. The results of this work suggest that the mechanism of the reaction involves the interaction of the neutral chloramine with the three ionic forms of sulfite, SO3-2, HSO3-, and H2SO3, with the rate of reaction increasing rapidly with increasing protonation. The estimated second-order rate constants for each ionic species as a function of temperature are \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm H}_{\rm 2} {\rm SO}_{\rm 3} } \hfill & {k_1 \, = \,2.00\, \times \,10^8 \,{\rm exp}\left( {{{ - 1544} \mathord{\left/ {\vphantom {{ - 1544} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right){\rm min}^{ - 1} } \hfill \\ {{\rm HSO}_{\rm 3}^ - } \hfill & {k_2 \, = \,4.35\, \times \,10^4 \,{\rm exp}\left( {{{ - 1170} \mathord{\left/ {\vphantom {{ - 1170} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right){\rm min}^{ - 1} } \hfill \\ {\,\,{\rm SO}_{\rm 3}^{ - 2} } \hfill & {k_3 \, = 1.58\, \times \,10^{12} \,{\rm exp}\left( {{{ - 12,660} \mathord{\left/ {\vphantom {{ - 12,660} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right){\rm min}^{ - 1} } \hfill \\ \end{array} $$\end{document} where the activation energies are in units of cal/mol.
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